21 research outputs found
Thermally Induced Oxidation of [FeII(tacn)2](OTf)2 (tacn = 1,4,7‐triazacyclononane)
Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/141624/1/ejic201701190_am.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141624/2/ejic201701190-sup-0001-SupMat.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/141624/3/ejic201701190.pd
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Silicon Carbide Micro-devices for Combustion Gas Sensing under Harsh Conditions
A sensor based on the wide bandgap semiconductor, silicon carbide (SiC), has been developed for the detection of combustion products in power plant environments. The sensor is a catalytic gate field effect device, Pt/SiO{sub 2}/SiC that can detect hydrogen-containing species in chemically reactive, high temperature (600 C) environments. We demonstrate that the device can be used as a hydrogen monitor in syngas applications of common interferants as well as sulfur and water vapor. These measurements were made in the Catalyst Screening Unit at NETL, Morgantown under atmospheric conditions. The sensor response to hydrogen gas at 350 C is 240 mV/decade, this is significantly higher than the device response to room temperature gas or that predicted from vacuum chamber studies. The enhanced catalytic activity of the platinum sensing film under energy plant operating conditions was investigated via AFM, x-ray diffraction, TEM and x-ray photoelectron spectroscopy. Our characterization indicated that exposure to high temperature gases significantly modifies the morphology of the Pt catalytic film and the Pt/SiO{sub 2} interfacial region, which we tentatively attribute to the enhanced hydrogen sensitivity of the sensing film. A model for the hydrogen/oxygen response of the SiC device under atmospheric conditions was developed. It is based on two independent phenomena: a chemically induced shift in the metal-semiconductor work function difference and the passivation/creation of charged states at the SiO{sub 2}-SiC interface. The optimum operating set point for the SiC sensor with respect to response time and long term reliability was determined to be close to mid-gap. Ultrahigh vacuum (UHV) techniques were used to investigate the effects of sulfur contamination on the Pt gate. Exposure to hydrogen sulfide, even in the presence of hydrogen or oxygen at partial pressures of 20-600 times greater than the H2S level, rapidly coated the gate with a monolayer of sulfur. Although hydrogen exposure could not remove the adsorbed sulfur, oxygen was effective at removing sulfur with no evidence of irreversible changes in device behavior. The role of oxygen in the functioning of the SiC sensors was also investigated. All of the results are consistent with oxygen acting through its surface reactions with hydrogen, including the need for oxygen to reset the device to a fully hydrogen-depleted state and competition between hydrogen oxidation and hydrogen diffusion to metal/oxide interface sites. A strong sensor response to the unsaturated linear hydrocarbon propene (C{sub 3}H{sub 6}) was observed
Silicon Carbide Micro-devices for Combustion Gas Sensing under Harsh Conditions
ABSTRACT A sensor based on the wide bandgap semiconductor, silicon carbide (SiC), has been developed for the detection of combustion products in power plant environments. The sensor is a catalytic gate field effect device that can detect hydrogen-containing species in chemically reactive, high temperature environments. For fast and stable sensor response measurements, a gate activation process is required. Activation of all sensors took place by switching back and forth between oxidizing (1.0 % oxygen in nitrogen) and reducing (10 % hydrogen in nitrogen) gases for several hours at a sensor temperature ≥620 °C. All 52 devices on the sensor chip were activated simultaneously by flooding the entire chip with gas. The effects of activation on surface morphology and structure of Pt gates before and after activation were investigated. The optical images obtained from Pt gates demonstrated a clear transition from a smooth and shiny surface to a grainy and cloudy surface morphology. XRD scans collected from Pt gates suggest the presence of an amorphous layer and species other than Pt (111) after activation. The reliability of the gate insulator of our metal-oxide-SiC sensors for long-term device operation at 630 °C was studied. We find that the dielectric is stable against breakdown due to electron injection from the substrate with gate leakage current densities as low at 5nA/cm 2 at 630 °C. We also designed and constructed a new nano-reactor capable of high gas flow rates at elevated pressure. Our reactor, which is a miniature version of an industrial reactor, is designed to heat the flowing gas up to 700 °C. Measurements in ultrahigh vacuum demonstrated that hydrogen sulfide readily deposits sulfur on the gate surface, even at the very high hydrogen/hydrogen sulfide ratios (10 3 -10 5 ) expected in applications. Once deposited, the sulfur adversely affects sensor response, and could not be removed by exposure to hydrogen at the temperatures and pressures accessible in the ultrahigh vacuum experiments. Oxygen exposures, however, were very effective at removing sulfur, and the device performance after sulfur removal was indistinguishable from performance before exposure to H 2 S.
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Silicon Carbide Micro-devices for Combustion Gas Sensing under Harsh Conditions
A sensor based on the wide bandgap semiconductor, silicon carbide (SiC), has been developed for the detection of combustion products in power plant environments. The sensor is a catalytic gate field effect device that can detect hydrogen-containing species in chemically reactive, high temperature environments. For fast and stable sensor response measurements, a gate activation process is required. Activation of all sensors took place by switching back and forth between oxidizing (1.0% oxygen in nitrogen) and reducing (10% hydrogen in nitrogen) gases for several hours at a sensor temperature {ge}620 C. All 52 devices on the sensor chip were activated simultaneously by flooding the entire chip with gas. The effects of activation on surface morphology and structure of Pt gates before and after activation were investigated. The optical images obtained from Pt gates demonstrated a clear transition from a smooth and shiny surface to a grainy and cloudy surface morphology. XRD scans collected from Pt gates suggest the presence of an amorphous layer and species other than Pt (111) after activation. The reliability of the gate insulator of our metal-oxide-SiC sensors for long-term device operation at 630 C was studied. We find that the dielectric is stable against breakdown due to electron injection from the substrate with gate leakage current densities as low at 5nA/cm{sup 2} at 630 C. We also designed and constructed a new nano-reactor capable of high gas flow rates at elevated pressure. Our reactor, which is a miniature version of an industrial reactor, is designed to heat the flowing gas up to 700 C. Measurements in ultrahigh vacuum demonstrated that hydrogen sulfide readily deposits sulfur on the gate surface, even at the very high hydrogen/hydrogen sulfide ratios (10{sup 3}-10{sup 5}) expected in applications. Once deposited, the sulfur adversely affects sensor response, and could not be removed by exposure to hydrogen at the temperatures and pressures accessible in the ultrahigh vacuum experiments. Oxygen exposures, however, were very effective at removing sulfur, and the device performance after sulfur removal was indistinguishable from performance before exposure to H{sub 2}S